EP1335892B1 - Verfahren zur herstellung von essigsäure - Google Patents

Verfahren zur herstellung von essigsäure Download PDF

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Publication number
EP1335892B1
EP1335892B1 EP01978426A EP01978426A EP1335892B1 EP 1335892 B1 EP1335892 B1 EP 1335892B1 EP 01978426 A EP01978426 A EP 01978426A EP 01978426 A EP01978426 A EP 01978426A EP 1335892 B1 EP1335892 B1 EP 1335892B1
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EP
European Patent Office
Prior art keywords
fluidized bed
reaction
range
acetic acid
stage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP01978426A
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German (de)
English (en)
French (fr)
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EP1335892A1 (de
Inventor
Sabine Zeyss
Uwe Dingerdissen
Manfred Baerns
Dorit Wolf
David Linke
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Celanese International Corp
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Celanese International Corp
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Publication of EP1335892A1 publication Critical patent/EP1335892A1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups

Definitions

  • the invention relates to a process for the preparation of acetic acid by oxidation of ethane with high selectivity and yield in fluidized bed reactors.
  • Catalytic gas phase oxidation of ethane to ethylene and acetic acid has been known for a long time.
  • the reaction is essentially influenced by the choice of reaction conditions, this is especially true for the selectivity of the reaction.
  • acetic acid is produced only as a by-product, the main product is ethylene, which may be further oxidized to carbon dioxide.
  • the object of the present invention was therefore to provide a process for the oxidation of ethane to acetic acid in a fluidized bed reactor, which can be operated with higher selectivity and thus greater yield than the processes described so far.
  • the selectivity of ethane oxidation to acetic acid depends on the size of the gas bubbles in the fluid catalyst fluidized bed.
  • bubble sizes of ⁇ 12cm are advantageous.
  • Particularly preferred are bubbles with a diameter of ⁇ 5cm.
  • Bubble sizes of ⁇ 12 cm can only be achieved by using catalyst particles with an average diameter of less than or equal to 80 ⁇ m.
  • the present invention accordingly relates to a process for the direct catalytic oxidation of ethane to acetic acid in a fluidized bed containing at least 70% of catalyst particles with a diameter of less than or equal to 80 microns.
  • the fluidized bed should also smaller Contain particles with a particle size of 10 to 60 microns, wherein the distribution of the particle size should be such that 10-60% of the particles should have a diameter below 60 ⁇ m.
  • Particularly preferred is a distribution of the particle size such that catalyst particles are in a diameter range of 10-40 ⁇ m width.
  • the diameter of 20-50% of the catalyst particles is less than 40 microns.
  • the fluid bed number to be set (the fluid bed number indicates the ratio between the set gas velocity and the minimum fluidization velocity) must be greater than one. That is, the fluidized bed must be in the fluid state. At a pressure of 16 bar and a temperature of 280 ° C results in a minimum fluidization speed at a particle diameter of 80 microns of 5.85 mm / s. Preferably, the fluidized bed number should be between 1 and 12.
  • Catalysts according to the general formula (I) have proved to be advantageous: M 0a Pd b X c Y d (I) wherein X is one or more of the elements selected from the group Cr, Mn, Nb, B, Ta, Ti, V, Te, W and Re and Y is one or more of the elements selected from the group B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Rh, Ir, Cu, Ag, Au, Fe, Ru, Cs, Mg, Ca , Sr, Ba, Li, K, Na, Rb, Be, Nb, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Tl, and U.
  • X and / or Y can also stand for several elements, it being possible for the indices c and d to assume different values for different elements.
  • the catalyst contains at least one of the following compositions in combination with oxygen: Mo 1.0 Pd 0.0005 V 0.25 Nb 0.12 Mo 1.00 Pd 0.0005 V 0.45 Nb 0.03 Sb 0.01 Ca 0.01 Mo 1.00 Pd 0.0005 V 0.45 Nb 0.03 Sb 0.01 Ca 0.01 K 0.05 Mo 1.00 Pd 0.00075 V 0.45 Nb 0.03 Sb 0.01 Ca 0.01 Mo 1.00 Pd 0.00075 V 0.55 Nb 0.03 Sb 0.01 Ca 0.01 Mo 1.00 Pd 0.00075 V 0.55 Nb 0.03 Sb 0.01 Ca 0.01 Mo 1.00 Pd 0.00075 V 0.45 Nb 0.06 Sb 0.01 Ca 0.01 Mo 1.00 Pd 0.0008 V 0.55 Nb 0.06 0.01 Sb0,01Ca Mo 1.00 Pd 0.00085 V 0.55 Nb 0.06 Sb 0.01 Ca 0.01 Mo 1.00 Pd 0.00075 V 0.55 Nb 0.09 Sb 0.01 ca 0.01 Mo 1.00 aPd 0.0008 V 0.50 Nb 0.15 Te 0.01
  • the reaction gas mixture may contain water vapor and inert gases such as nitrogen or carbon dioxide.
  • water vapor accelerates the oxidation of ethane to acetic acid at the expense of the oxidation of ethane to ethylene and thus results in an increase in the selectivity to acetic acid.
  • the process is preferably carried out at low temperatures.
  • Low temperatures increase the selectivity of the oxidation reaction Favor of acetic acid.
  • a temperature range of 100 to 500 ° C at a reactor pressure of 1 to 50 bar are preferred.
  • the density of the catalyst particles can be between 500 and 6000 kg / m 3 .
  • To carry out the method can, for.
  • As a fluidized bed reactor can be used, as described in US 5,300,684.
  • the inventive method has a high selectivity, accordingly, increased space-time yields in the oxidation of ethane to acetic acid in a fluidized bed reactor, can be achieved at moderate temperatures. Furthermore, the disturbing backmixing of the reactants in the fluidized bed can be reduced by reducing the size of the bubbles. This also leads to an increased selectivity of the reaction, whereby the space-time yield of acetic acid increases.
  • the reaction can be carried out in the multi-stage fluidized bed reactor with its own gas supply to each stage. Bubble growth begins again at each stage, so that on average smaller bubbles are achieved than in a single-stage fluidized bed.
  • the small bubbles can also by internals, such. As grids are achieved in the fluidized bed.
  • a more extensive distributed oxygen supply into individual stages can be advantageous.
  • the advantageous bubble sizes in a fluid fluidized bed and the corresponding reaction parameters were determined from measurement results obtained in investigations of the catalytic gas-phase oxidation of ethane in a fixed bed.
  • the kinetic parameters determined for the underlying reaction are summarized in FIGS. 1a and 1b.
  • the Catalytic gas-phase oxidation of ethane is mediated by two different catalytically active sites Z and X of the catalyst.
  • Z represents a site at which all oxidation steps take place, namely the oxidative dehydrogenation of ethane, the partial and the complete oxidation of ethene and of acetic acid.
  • X is a position on the catalyst that only becomes active in the presence of water.
  • the activated form of X leads to the conversion of ethene to acetic acid via a mechanism similar to the Wacker reaction.
  • the formation of acetic acid thus takes place via two different reaction pathways - via the partial oxidation of ethene at the position Z (step 2 in FIG. 1 a) and via a mechanism similar to the Wacker reaction at position X (step 3 in FIG ).
  • the required kinetic values for the intermediates on the catalytic surface during the steady-state Z, Z-OH 2 , ZO, Z-CH 2 H 4 , X-OHOH and XO were determined analytically and are given in Table X.
  • the values determined in this way were used to simulate the fluidized-bed reactor according to the bubble assembly model (BAM) (K. Kato, CH Wen, Chem. Eng. Sci., 24, 1331-1368 (1969)).
  • the model describes the fluidized bed as a two-phase system consisting of a catalyst-deficient bubble phase and a catalyst-rich emulsion phase; the two-phase structure of such a reaction mixture of particles in a fluidized fluidized bed with gas supply can be verified with the naked eye. Since the emulsion phase contains a large proportion of solid, there takes place the catalytic reaction, while in the bubble phase due to the low concentration of the catalytic material almost no reaction takes place.
  • the model of the fluidized bed reactor must therefore describe the transition of reactants and products between the bubble and the emulsion phase and at the same time take into account the growth of the bubbles with increasing distance from the gas distributor, an effect well known from fluidized fluidized beds. For this reason, the fluidized bed was divided into segments with the height corresponding to the local Bubble diameter corresponds. The bubble diameter, the velocity of the bubbles, the expansion of the bed, and the local volume fractions of the phases were determined by Werther (J. Werther, Chem. Eng. Sci. 47 (9-11), 2457-2462 (1992)) and Murray (JD Murray, J. Fluid., Mech., 21, 465 (1965)). For both, bubble and emulsion phases, each segment was described as an ideal stirred tank. Isothermal reaction conditions can be approximately adjusted due to the good heat removal from fluidized bed reactors; therefore the reactor was considered isothermal in the modeling.
  • K BE, i, k can be quantitatively determined by a correlation of Sit and Grace (SP, Sit, JR Grace, Chem. Eng. Sci. 36, 327-335 (1981)).
  • the minimum fluidized bed velocity u mf is determined as described in Wen et al. (CY Wen, YH Yu, AIChE J. 12, 610 (1966)).
  • the direct catalytic oxidation of ethane to acetic acid in a fluidized fluidized bed can be largely described.
  • the present calculations were carried out assuming a reactor diameter D i of 4 m, a particle size of 60 microns and 80 microns (according to the money class classification A), a density of the particles of 3100 kg / m 3 and a porosity of the fluidized bed reactor of 0 , 5 at minimal fluidization speed.
  • the corresponding minimum fluidization speed was 3.3 m / s (at 60 ⁇ m) and 5.85 m / s (at 80 ⁇ m).
  • the gas distributor was assumed to be a nozzle plate distributor with 800 openings per m 2 .
  • each stage was modeled as a single fluidized bed reactor with its own gas distributor.
  • the same oxygen stream is added to the gas stream prior to each stage.
  • the volume flow increases from stage to stage, so that the fluidized bed number increases slightly from 7.5 to 8.5.
  • the example shows that with a maximum bubble size d B of 1 cm in the fluidized bed reactor and fixed bed reactor almost identical results regarding the selectivity to acetic acid and the space-time yield are obtained because this bubble size virtually no inhibition of mass transfer between bubbles and emulsion phase occurs and additionally Backmixing is reduced.
  • the low selectivity and space-time yield is due, at least in part, to the undesirable backmixing in the fluidized bed and to the slow mass transfer between the bubble and the emulsion phase which causes the oxygen from the bubbles to flow only slowly into the Emulsion phase passes.
  • a high oxygen concentration in the bubbles additionally leads to increased formation of carbon dioxide due to unselective further oxidation of the acetic acid and thus to a reduction in acetic acid selectivity.
  • Table 1 Sales and Selectivity Data for Influence of Bubble Size and Particle Diameter, respectively (Figs. 3 and 4) ⁇ m / kg ⁇ s ⁇ m -3 X C2H6 /% X O2 /% S C2H4 /% S HOac /% S CO2 /% 60 ⁇ m particle diameter 7540 1.19 11.19 0.28 80.33 19.39 15080 2.22 21.29 0.22 78.80 20.99 30159 3.88 37,99 0.30 76.67 23,03 60318 5.92 58.88 1.17 73.79 25,04 90477 7.13 71.35 1.77 72.28 25.94 150795 8.51 85.52 2.47 70.78 26.75 226193 9,31 93.75 2.91 69.96 27.13 301591 9.66 97.30 3.11 69.61 27.27 80 ⁇ m particle diameter 4250 0.69 6.44 0.38 81.25 18.37 8499 1.31 12.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP01978426A 2000-11-10 2001-10-17 Verfahren zur herstellung von essigsäure Expired - Lifetime EP1335892B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10055810A DE10055810A1 (de) 2000-11-10 2000-11-10 Verfahren zur Herstellung von Essigsäure
DE10055810 2000-11-10
PCT/EP2001/012001 WO2002038526A1 (de) 2000-11-10 2001-10-17 Verfahren zur herstellung von essigsäure

Publications (2)

Publication Number Publication Date
EP1335892A1 EP1335892A1 (de) 2003-08-20
EP1335892B1 true EP1335892B1 (de) 2006-05-17

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP01978426A Expired - Lifetime EP1335892B1 (de) 2000-11-10 2001-10-17 Verfahren zur herstellung von essigsäure

Country Status (24)

Country Link
US (1) US6906221B2 (ko)
EP (1) EP1335892B1 (ko)
JP (1) JP2004513157A (ko)
KR (1) KR100605241B1 (ko)
CN (1) CN1224599C (ko)
AT (1) ATE326442T1 (ko)
AU (2) AU1054702A (ko)
BR (1) BR0115224B1 (ko)
CA (1) CA2428308C (ko)
CZ (1) CZ304601B6 (ko)
DE (2) DE10055810A1 (ko)
ES (1) ES2264991T3 (ko)
HK (1) HK1068869A1 (ko)
MX (1) MXPA03004115A (ko)
MY (1) MY129074A (ko)
NO (1) NO328033B1 (ko)
NZ (1) NZ525383A (ko)
PL (1) PL203045B1 (ko)
RS (1) RS50361B (ko)
RU (1) RU2245323C1 (ko)
TR (1) TR200300611T2 (ko)
UA (1) UA73815C2 (ko)
WO (1) WO2002038526A1 (ko)
ZA (1) ZA200303064B (ko)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080096686A (ko) * 2006-02-07 2008-10-31 셀라니즈 인터내셔날 코포레이션 에탄-기재 공정에서 에탄으로부터 에틸렌을 분리하여 아세트산을 제조하기 위한 화학 반응의 용도
US20110178333A1 (en) * 2008-06-10 2011-07-21 Lg Chem, Ltd. Catalyst for gas-phase contact oxidation of hydrocarbon, preparation method thereof and gas-phase oxidation method of hydrocarbon using the same
US20110178332A1 (en) * 2008-06-10 2011-07-21 Lg Chem, Ltd Catalyst for gas-phase contact oxidation of hydrocarbon, preparation method thereof and gas-phase oxidation method of hydrocarbon using the same
RU2400298C2 (ru) * 2008-11-01 2010-09-27 Леонид Модестович Кустов Катализатор окисления
CA2832887A1 (en) 2011-04-11 2012-10-18 ADA-ES, Inc. Fluidized bed method and system for gas component capture
IN2015DN02082A (ko) 2012-09-20 2015-08-14 Ada Es Inc
US20140275619A1 (en) 2013-03-15 2014-09-18 Celanese International Corporation Process for Producing Acetic Acid and/or Ethanol By Methane Oxidation
ES2867879T3 (es) * 2018-05-15 2021-10-21 Daicel Corp Método de producción de ácido acético

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988004199A1 (en) 1986-12-10 1988-06-16 Lummus Crest, Inc. Fluidized bed
US5300684A (en) * 1991-12-09 1994-04-05 The Standard Oil Company Process for the fluidized bed oxidation of ethane to acetic acid
DE19620542A1 (de) * 1996-05-22 1997-11-27 Hoechst Ag Verfahren zur selektiven Herstellung von Essigsäure
DE19630832A1 (de) * 1996-07-31 1998-02-05 Hoechst Ag Verfahren zur selektiven Herstellung von Essigsäure
GB9819221D0 (en) 1998-09-04 1998-10-28 Bp Chem Int Ltd Process for the production of acetic acid

Also Published As

Publication number Publication date
TR200300611T2 (tr) 2003-09-22
AU2002210547B2 (en) 2005-04-07
PL361422A1 (en) 2004-10-04
BR0115224A (pt) 2003-10-07
UA73815C2 (en) 2005-09-15
NO328033B1 (no) 2009-11-10
NZ525383A (en) 2004-10-29
HK1068869A1 (en) 2005-05-06
DE50109832D1 (de) 2006-06-22
RS50361B (sr) 2009-11-10
KR100605241B1 (ko) 2006-07-28
MXPA03004115A (es) 2003-08-19
CN1224599C (zh) 2005-10-26
RU2245323C1 (ru) 2005-01-27
CZ304601B6 (cs) 2014-07-30
NO20032098L (no) 2003-05-30
JP2004513157A (ja) 2004-04-30
WO2002038526A1 (de) 2002-05-16
CA2428308C (en) 2009-08-18
CA2428308A1 (en) 2002-05-16
ATE326442T1 (de) 2006-06-15
DE10055810A1 (de) 2002-05-23
AU1054702A (en) 2002-05-21
EP1335892A1 (de) 2003-08-20
US20040133039A1 (en) 2004-07-08
MY129074A (en) 2007-03-30
CZ20031261A3 (cs) 2003-08-13
ES2264991T3 (es) 2007-02-01
US6906221B2 (en) 2005-06-14
PL203045B1 (pl) 2009-08-31
BR0115224B1 (pt) 2012-07-24
YU31103A (sh) 2006-08-17
ZA200303064B (en) 2004-05-20
KR20030048468A (ko) 2003-06-19
CN1535259A (zh) 2004-10-06
NO20032098D0 (no) 2003-05-09

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